Emulsions Useful for Coatings and Coating Additives

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to methods of preparing emulsions for coating compositions and coating additives, to the resulting compositions and additives, and to their use.

2. Related Art

In an increasing number of industries, aqueous coating compositions continue to replace traditional organic solvent-based coating compositions. Paints, primers, stains, sealants, and adhesives, for example, previously formulated with organic solvents are now formulated as aqueous compositions. This reduces potentially harmful exposure to volatile organic compounds (VOC's) commonly found in organic solvent-based compositions. The need to meet or exceed such performance standards places a premium on the characteristics and properties of such aqueous coating compositions.

Thus, there is a continuing need for compositions that maintain solvent-like application and performance properties, with reduced VOC content.

SUMMARY OF THE INVENTION

The invention provides aqueous coating compositions for application to a substrate, in the form of an emulsion. The aqueous coating composition includes an organic phase having a substrate coating resin, an aqueous phase (which can be an aqueous emulsion, dispersion, or solution), and an emulsifier in an amount sufficient to emulsify the organic and aqueous phases. The invention also provides methods of making the compositions, as well as applying such compositions to substrates.

The invention also provides aqueous coating additives that can be added to coating compositions, in the form of an emulsion. An aqueous coating additive includes an organic phase having a hydrophobic additive, an aqueous phase (which can be an aqueous emulsion, dispersion, or solution), and an emulsifier in an amount sufficient to emulsify the organic and aqueous phases. The invention also provides methods of making the coating additives, as well as use of such additives in coating compositions.

In embodiments of the invention, the emulsifier includes a polyolefin aminoester, a substituted alkanolamine, or a mixture thereof. In other embodiments, the emulsifier includes a polyalkylene glycol ether. In still yet other embodiments, the emulsifier includes Videt ME-80 anionic emulsifier.

The aqueous coating compositions and additives of the invention are advantageous in forming emulsions with hydrophobic media, including resins and additives that cannot typically be used in an aqueous environment. Further, compositions of the invention maintain solvent-like application and performance properties, with reduced VOC content compared to non-aqueous compositions.

Illustrative coating compositions include emulsions containing hydrophobic resins useful as sizing, coating, staining, priming, or textile resins and treatments. Descriptive additives that can be used in the present invention include waxes, silicones, fluorocarbons, and UV absorbers, and more generally for any additive that is not typically soluble in water.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides emulsions of an aqueous phase and an organic phase, which are useful as coatings and coating additives with reduced VOC content.

In an embodiment of the invention, an aqueous coating composition is provided. The aqueous coating composition includes an organic phase comprising a substrate coating resin, an aqueous phase, and an amount of an emulsifier sufficient to emulsify the aqueous and organic phases.

The term “aqueous coating composition” is intended to encompass compositions containing an aqueous phase (e.g., water) that are applied to substrates. Illustrative coatings that can utilize the composition of the invention include wood coatings such as, e.g., stains, seal coat/sealers, topcoats, wiping stains, glazes, and fillers. Examples of other coatings include paints (e.g., house paints), primers, architectural coatings, industrial coatings, maintenance coatings, general metal-type coatings, paper coatings including textile treatments, plastics coatings such as primers, base coats, top coats, and adhesion promoters, and polishes. Other suitable coatings that are embodied by the aqueous coating compositions of the invention can be found in “Paint & Ink Formulations Database” by Earnest W. Flick, 2005; William Andrew—publisher; ISBN: 0815515081; and Paint and Surface Coatings: Theory and Practice, 2^nd Ed. By R. Lambourne and T. A. Striven, eds., 1999; William Andrew—publisher; ISBN: 18884207731; and “Organic Coatings: Science and Technology, 2^nd Ed; by Zeno W. Wicks, Frank N. Jones, and S. Peter Pappas, 1999; —Wiley-Interscience; ISBN:0471245070, all incorporated by reference herein.

The term “substrate coating resin” is intended to encompass hydrophobic resins that can be incorporated into aqueous compositions of the invention that are suitable for coating a substrate. Suitable resins include but are not limited to one or more of a silicone-modified polymer, a perfluorinated polymer, a chlorinated polyolefin, a nonchlorinated polyolefin, a hydroxyl-functional polymer, an acrylic, a polyester, a modified polyester (e.g., amine-modified), a polyether, an acrylate-functional resin, an acrylated acrylic, an acrylated polyester, an acrylated polyether, an acrylated polyurethane, an acrylated epoxy, an amine-modified acrylated acrylic, an amine-modified polyether, an unsaturated polyester, an allyl-functional polymer, styrene allyl alcohol, a non-water soluble polyol, an air-oxidizable initiator/crosslinker, a phenoplast resin, an aminoplast resin, an oil, a fat, a fatty acid, a resin derived from an oil, fat, or fatty acid, a plasticizer, a hydroxyl-terminated polybutadiene resin or derivative thereof, a maleic-modified resin, an ethylene vinyl acetate copolymer, a styrene-butadiene copolymer, a styrene-isoprene copolymer, an acrylic copolymer, a butadiene-based polymer, an alkyd resin, a modified alkyd resin including styrene, vinyl toluene and urethane-modified alkyds, and an aliphatic or aromatic hydrocarbon resin.

Suitable oils and fats and resins derived there from that can be used as part of the substrate coating resin of the invention include those described in Bailey's Industrial Oil and Fat Products, Volume 1, 4th edition, edited by Daniel Swern, copyright John Wiley and Sons; ISBN: 0-471-83957-4.

In another embodiment of the invention, an aqueous coating additive is provided. The additive includes an organic phase having one or more hydrophobic additives, an aqueous phase, and an amount of an emulsifier sufficient to emulsify the aqueous and organic phases.

The hydrophobic additives that can be used in the aqueous coating additive of the invention include photoinitiators, defoamers (e.g., silicone), antioxidants, waxes, colorants, pigments, dyes, rheology modifiers, anti-settling agents, dispersants, antimar agents, UV absorbers, light stabilizers, catalysts, crosslinkers, redox catalysts, flow and leveling agents, wetting agents, catalysts, sunscreens, biocides, plasticizers, and water repellants. Other suitable hydrophobic additives that can be used in the aqueous coating additive of the invention are described in the textbook Handbook of Coatings Additives, 2^nd Ed. By John J. Florio and Daniel J. Miller, eds., 2004; publisher Marcel Dekker; ISBN: 0824756266; and Additives for Coatings by Johan Bieleman, ed., 2000; Publisher—Wiley—VCH; ISBN: 3527297855, which are incorporated by reference herein.

Other hydrophobic moieties that can be incorporated into the aqueous coating compositions and additives according to the invention include the resins and additives described on pages 10-15 of International Publication No. WO 2004/030801, such as, for example, different types of silicones, waxes, chlorinated polymers, polyols/hydroxy functional polymers, unsaturated and UV-curable resins and oligomers, photoinitiators/additive stabilizers, and aminoplast and phenoplast resins. Page 10, line 1 to p. 15, line 18 of WO 2004/030801 is specifically incorporated by reference herein.

The aqueous phase of the coating compositions and coating additives of the invention is typically water, but may also include components which are soluble in and/or dissolved in and/or dispersed into water or an aqueous phase. Such components include but are not limited to catalysts, salts, polymers, dyes, and pigments. The aqueous phase may also include a water-co-solvent blend.

For example, one or more pigments may be dispersed in the aqueous phase of the coating compositions of the invention. The types of pigments that can be used in the invention are not particularly limited and are known to those skilled in the art. Illustrative pigments include titanium dioxide, silica, silicates such as aluminum silicate and sodium potassium alumino silicate. Other pigments that can be used in the invention are described in the textbook Pigment Handbook, Properties and Economics, 2^nd ed. By Peter A. Lewis (Editor), Wiley-Interscience; 2^nd edition, 1988, ISBN: 0471828335, incorporated by reference herein.

The aqueous phase containing the one or more pigments may also include wetting and/or dispersing agents. Illustrative wetting and dispersing agents include, but are not limited to modified acetylenic diols and pigment wetting and dispersing agents such as those manufactured by Air Products and Chemicals (Allentown, Pa.), alkyl phenol ethoxylates, alcohol ethoxylates, sulfosuccinates, sulfates and sulfonates such as those manufactured by Union Carbide/Dow Chemical, (Midland, Mich.), and high molecular weight wetting and dispersing additives such as the Disperbyk line marketed by Byk-Chemie USA (Wallingford, Conn.) (for example Disperbyk 190, 191, and 194). Other wetting and dispersing aids (including surfactants) useful for the invention include those mentioned in the books “Surfactants and Interfacial Phenomena” by Milton J. Rosen, Wiley-Interscience; 3rd edition, 2004; ISBN: 0471478180 and “Surfactants: Chemistry, Interfacial Properties, Applications (Studies in Interface Science)” by D. Möbius, R. Miller, V. B. Fainerman, Elsevier Science; Bk&CD-Rom edition, 2001; ISBN: 0444509623, and “Performance Enhancement in Coatings by Edward W. Orr, Hanser Publishers, Munich, 1998; ISBN: 3-446-19405-3 all incorporated herein for reference.

In an embodiment of the invention, the aqueous phase is in itself an emulsion. In a “dual emulsion” of the invention, in the presence of a hydrophobic material (e.g., a chlorinated polyolefin), instead of emulsifying water, another emulsion is emulsified, such as an aqueous latex or acrylic emulsion. Such a dual emulsion enables the performance properties of a very high molecular weight latex to be delivered to a substrate with the application properties of a solution coating. A dual emulsion also enables water soluble items (such as catalysts, or reactive moieties, for example) to be delivered to a substrate in the presence of a reactive polymer, all in the same package.

Latexes, dispersions, and emulsions that may be incorporated into the dual emulsion are not particularly limited. Illustrative latexes include an acrylate-styrene copolymer, straight acrylics, vinyl acrylics, latexes based on vinyl esters of the C9-C11 versatic acids, vinyl acetate-based emulsions, vinyl chloride acrylic copolymers, vinylidine chloride terpolymers, styrene-butadiene copolymers, polyurethane dispersions, polyurethane-acrylic hybrids, and self-crosslinking latexes. Both emulsions and dispersions (such as alkyd dispersions) are useful as part of the dual emulsion. Specific examples include styrene acrylic emulsion H595 (Alberdingk Boley; Greensboro, N.C.), acrylic emulsion AC2538 (Alberdingk Boley); CR712 acrylic emulsion (Noveon; Cleveland, Ohio); Rhoshield 3188 self-crosslinking emulsion (Rohm and Haas Co.; Philadelphia, Pa.); and polyurethane dispersions Sancure 843 (Noveon) and Hybridur 570 (Air Products and Chemicals; Allentown, Pa.).

The emulsifier used in the aqueous coating compositions and additives of the invention can be one or more of the emulsifiers described on page 12, line 14 through page 27, line 11 of International Publication No. WO 2004/055137, the publication incorporated herein by reference. Also, the emulsifier used in the compositions of the invention can include one or more of the emulsifiers or dispersants disclosed in, and more specifically the polyisobutenyl aminosuccinate derivative emulsifiers or dispersants disclosed in, U.S. Pat. Nos. 6,783,746; 6,780,209; 6,770,605; 6,648,929; 6,368,367; 6,383,237; 6,280,485; 6,165,235; and 5,885,944; all incorporated by reference herein.

Preferably, the emulsifier used in the compositions and additives of the invention is a polyolefin aminoester, a substituted alkanolamine, or a mixture thereof. Suitable emulsifiers include ethanoldiethonium polyisobutenyl triethylaminosuccinate, TEA-diethanolaminoethyl polyisobutenyl succinate, glyceryl polyisobutenyl succinate, or mixtures thereof. For example, ethanoldiethonium polyisobutenyl triethylaminosuccinate available under the trade name Chemccinate® 5603, TEA-diethanolaminoethyl polyisobutenyl succinate and ethylhexyl palmitate succan-based emulsifier available under the trade name Chemccinate® 2000, glyceryl polyisobutenyl succinate and ethylhexyl palmitate and glycerin succan-based emulsifier available under the trade name Chemccinate® 1000AF, all from Chemron Corporation (Paso Robeles, Calif.), or mixtures thereof are suitable emulsifiers for the compositions and additives of the invention.

In another embodiment of the invention, the emulsifier is a polyalkylene glycol ether having a molecular weight of about 2000 to about 4000. An illustrative polyalkylene glycol ether for use in the compositions and additives of the invention is an alkyl ethylene oxide/propylene oxide copolymer having a molecular weight of about 3000, such as Tergitol® XD available from Dow/Union Carbide, Houston, Tex.

In yet another embodiment of the invention, the emulsifier is the orange oil anionic emulsifier Videt ME-80, available from Vitech International Inc., Janesville, Wis.

The amounts of the organic phase, aqueous phase, and emulsifier in the aqueous coatings and additives of the invention are not particularly limited and will depend upon, e.g., the desired properties of the coating or additive. Illustratively, the aqueous coating composition or additive can contain, by weight of the composition, about 5% to about 60% of an organic phase, about 1% to about 95% of an aqueous phase, and about 0.5% to about 30% by weight of an emulsifier.

The aqueous compositions and additives of the invention can be prepared by combining a hydrophobic or organic phase, an aqueous phase, and an emulsifier, and forming an emulsion according to methods known by those skilled in the art.

In an embodiment, the emulsifier or mixture of emulsifiers is mixed into or dissolved in a compatible solvent and/or the hydrophobic moiety. Additional additives or chemicals are added as required to build any special end use and/or application property. Water may then added under shear or agitation to prepare an emulsion.

The viscosity of the hydrophobic resin or additive can be reduced by the addition of a solvent prior to preparation of the emulsion. Alternatively or additionally, the resin or additive can be solubilized. Suitable solvents include but are not limited to aliphatic hydrocarbons, such as, for example, White Spirit, isooctane, cyclopentane, and cyclohexane, methylcyclohexane, dipentene, and turpentine; aromatic hydrocarbons, such as, for example aromatic 100, 150, and 200, toluene, and xylenes; esters, ketones such as, for example cyclohexanone, 2-heptanone, and methyl-isobutyl ketone; ethers, parachlorobenzotrifluoride, and chlorinated solvents. Other suitable solvents include those listed in the Handbook of Solvents by George Wypych, ed., 2001; Publisher—ChemTec Publishing; ISBN: 0815514581; and Surface Coatings: Science and Technology, 2^nd Ed. By Paul Swaraj, 1996; Publisher—John Wiley & Sons; ISBN: 0471958182, which are incorporated by reference herein.

When a solvent is used, the aqueous coating compositions and coating additives are preferably prepared by combining the solvent, the aqueous phase, and the emulsifier to form an emulsion, and subsequently adding the resin or additive. However, a resin or additive may be dissolved with the solvent, with one or more additional resins being added after the emulsion is formed.

In embodiments of the invention, the aqueous compositions and additives form a water-in-oil emulsion. For example, a water-in-oil emulsion is typically formed when the emulsifier used includes a polyolefin aminoester, a substituted alkanolamine, or a mixture thereof, or Videt ME-80.

In other embodiments of the invention, the aqueous compositions and additives form an oil-in-water emulsion. For example, an oil-in-water emulsion is typically formed when the emulsifier used includes a polyalkylene glycol ether such as Tergitol® XD.

An illustrative aqueous coating composition or coating additive is formed by combining a chlorinated polyolefin dissolved in a solvent with the aqueous phase and an emulsifier and agitating to form an emulsion, and adding an additional resin or additive. Use of a chlorinated polyolefin in aqueous coating compositions and coating additives of the invention improves emulsion properties and results in an enhanced cure, particularly when used with UV-curable materials.

As mentioned above, the compositions and coating additives of the invention are particularly useful for and intended for application to a substrate, to produce articles of manufacture with the composition applied thereto. Illustrative substrates to which the compositions of the invention can be applied include wood, composites, textiles and nonwovens, paper, exterior siding, sheetrock, and any other substrate for which a coating might be useful.

Illustrative applications of the invention include stains (e.g. a deck stain), adhesion promoters to plastic (e.g. to thermoplastic olefin plastic (TPO)), paints, primers, and other coatings. Other applications of the invention are described in the Examples, below.

Stains and primers of the invention include an organic phase, an aqueous phase, and an emulsifier as described above. The organic phase can include a resin and/or a solvent, and optionally one or more additives.

Resins used in the stains and primers of the invention include but are not limited to alkyds, including soya oil-modified (long, medium, and short-soya), linseed oil-modified, tung oil-modified, coconut oil-modified, tall oil-modified, palm-oil-modified, castor-oil modified, avocado oil-modified, canola oil-modified, corn oil-modified, fish oil-modified, peanut oil-modified, rapeseed oil-modified, safflower oil-modified, sunflower oil-modified, walnut oil-modified, styrenated, vinyl-modified, urethane-modified, and silicone-modified alkyds; oil-modified urethanes; fats and oils such as soya oil, corn oil, sunflower oil, coconut oil, linseed oil, cottonseed oil, olive oil, tung oil, fish oil, peanut oil, and the like; oil-modified acrylics and the like; rosin and rosin esters; maleic-modified resins and the like; plasticizers, hydroxyl terminated polybutadiene resins and derivatives thereof; aromatic and aliphatic hydrocarbon resins such as, for example the Polybd and Norsolenen series of resins available from Sartomer Co, Exton, Pa. or the Petrorez and Pentrex brand polymers available from Lawter International Pleasant Prairie, Wis., and the Unirez brand resins available from Union Camp, Savannah, Ga.

Suitable solvents for stains and primers of the invention include but are not limited to aliphatic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, parachlorobenzotrifluoride, and plasticizers.

Additives for the stains and primers of the invention include, but are not limited to, the additives described above; particularly, colorants, pigments, dyes, rheology modifiers, anti-settling agents, dispersants, antimar agents, UV absorbers, light stabilizers, antioxidants, metal complexation catalysts and crosslinkers, redox catalysts, flow and leveling agents, wetting agents, defoamers, catalysts, sunscreens, biocides, water repellants, waxes, and plasticizers.

Stains of the invention are capable of being used over bare wood or over washcoats and sealers and topcoats, without loss of finish clarity or appearance. The stains also exhibit desirable properties such as reduced grain raising and good water resistance.

An embodiment of the invention is directed to an aqueous adhesion promoter composition. The adhesion promoter composition includes an organic phase, an aqueous phase, and an emulsifier as described above. Typically, the organic continuous phase includes a solvent and a resin or additive including a chlorinated polyolefin. Use of a chlorinated polyolefin provides adhesion properties to the composition which are particularly useful in coating plastics such as thermoplastic polyolefins (TPOs), polyethylene and polyethylene composites such as decking materials and fences, polypropylene, polypropylene composites, wood plastic composites, and the like. However, a non-chlorinated polyolefin such as, for example AP 440-1 (Eastman Chemical Co., Kingsport, Tenn.) is also suitable.

Compositions and additives of the present invention have reduced volatile organic compound (VOC) content compared to conventional formulations, while maintaining solvent-like application and appearance properties. The reduction in VOC content depends on, e.g., the coating type and technology used therein. For example, the VOC content in the compositions, particularly for stains of the invention, can range from about 0 lbs/gal to about 4.0 lbs/gal of the formulation, preferably about 0.15 lbs/gal VOC to about 2.0 lbs/gal VOC.

The following examples are provided to further illustrate the present invention. It is to be understood, however, that these examples are for purposes of illustration only and are not intended as a definition of the limits of the invention.

EXAMPLES

Examples 1-4 illustrate development of a resin or resin intermediate based on an oil modified polyurethane blended with the aminoester and/or a substituted alkanolamine, and subsequent low VOC deck stain development.

Example 1. Example of Resin and/or Intermediate

	Item	Wt/lbs

	Solvent 150	8.9
	Paraffin Wax R2531	0.28
	Lubrizol 47550 AF	0.84
	Irganox 1010	0.028

	Heated to 100-110° F. Mixed until dissolved, then added
	under agitation

	Foamtrol 110	0.42
	PolyFox PF3320	0.12
	Urotuff 19M50	5.65

Example 2. Example of Resin and/or

Intermediate and/or Formulation

	Item	Wt/lbs

	Example 1	16.238
	Busan 1105	0.28
	Tinuvin 1130	0.07
	Michelman 433	0.14
	Hombitec RM401LP	0.99

	Mixed well

Example 3. Example of Intermediate

and/or Formulation and/or Stain

	Item	Wt/lbs

Example 2

17.718

	Added the following slowly under very
	good agitation and shear

	Water	21.52

Example 4. Example of Intermediate

and/or Formulation and/or Stain

Item	Wt/lbs

Example 3

39.23

Tinted with

Tint-AYD AL600	0.42
Tint-AYD AL499	0.70
Calculated VOC	31.3% VOC; 2.52 lbs VOC/gal
Viscosity, RVDVE, sp4, 100 rpm	304 cps
Application and appearance	Excellent

The composition of Example 1 is useful as a resin intermediate containing the surfactant, while the composition of Example 4 is useful as a low VOC deck stain.

The composition of Example 4 was compared to two commercial deck stains for water absorption; CWF-UV clear wood finish, manufactured by the Flood Company, Hudson, Ohio, and Cuprinol Redwood UV Sunblock deck and wood seal, manufactured by the Sherwin Williams Company, Cleveland, Ohio, by dipping followed by brushing pre-treated pine fence parts (from the same fence post). The entire 3.5 in×3.5 in part was coated, including the edges. 4.7 grams of the composition of Example 4 was applied to the wood part, while 4.90 grams and 4.53 grams of stain was applied to the wood parts with CWF-UV and Cuprinol stains respectively. A 4th wood part was left uncoated. After 5 days, the coated wood parts were submerged into a water bath for 1 hour. The bare wood absorbed 8.65% water. The CWF-UV and the Cuprinol Redwood stains absorbed 8% and 5.95% water respectively. The stain of Example 4 absorbed 4.9% water.

Example 5 details development of a stain with low viscosity and improved flow.

Example 5. Example of Deck Stain Formulation

With Low Viscosity and Improved Flow

	Item	Wt/grams

	Solvesso 150	47
	Paraffin R2531	2
	Mineral Spirits 66/3	17
	Lubrizol 47550 AF	6
	Irganox 1010	0.2

Heated at 110° F. and mixed until dissolved

	Foamtrol 110	3
	PolyFox PF3320	0.85
	UROTUFF 19M50	40
	Michem Wax 433	1
	Hombitec RM401LP	7
	Tinuvin 1130	0.5
	Busan 1105	2

	Mixed 10 to 15 min, then added with good
	agitation

Water

150

Then added

	Tint-AYD AL600	3.0
	Tint-AYD AL499	5.0
	Solvesso 150	4.7
	BYK333	2
	Viscosity, #4 spindle, cps	208

The stain of Example 5 was compared to commercial stains, CWF-UV and Cuprinol Redwood, by application onto 4 in×4 in pieces of picket fence parts. The entire part was coated with stain by dipping and brushing. The stains were allowed to air dry for 4 hours. The parts were then submerged into a water bath for 1 hour, along with an uncoated part. Table 1 details stain loading and water resistance results.

TABLE 1
Comparison of Example 5 Stain to Commercial
Stains for Early Water resistance

	Wet Stain	% Water
Stain	Loading	Absorption	Comments
Example 5 Stain	4.6 grams	10.26	No visual change in
			wood dimensions
Bare Wood	N/A	32.38	Wood swells and cups
Cuprinol Redwood	3.98 grams	12.73	Wood swells and cups
Commercial Stain
CWF-UV Clear	3.87 grams	24.89	Wood swells and cups
Wood Finish
commercial Stain

The results of Table 1 show that the Example 5 stain penetrates the wood to a greater degree and result in improved early water resistance as compared to the commercial stains.

Examples 6 and 7 detail development of a natural deck stain.

Example 6. Example of Gilsonite Solution for

Incorporation in Low VOC Natural Deck Stain

	Item	Wt/grams

	Solvesso 150	225
	Gilsonite ER125	75

	Stirred until dissolved with some heating

Example 7. Example of Natural Deck Stain Formulation

	Item	Wt/grams

	Solvesso 150	63
	Paraffin R2531	2
	Lubrizol 47550 AF	6
	Irganox 1010	0.2

Heated at 110° F. and mixed until dissolved

	Foamtrol 110	3
	PolyFox PF3320	0.85
	UROTUFF 19M50	40
	Michem Wax 433	1
	Hombitec RM401LP	7
	Tinuvin 1130	0.5
	Busan 1105	2

	Mixed 10 to 15 min, then added with good
	agitation

Water

150

Then added

	Tint-AYD AL499	1.59
	Tint-AYD AL505	0.61

	Tinted to color with Example 6

The formulations of Example 7 was compared to a commercial natural deck stain, CWF-UV manufactured by the Flood Company, Hudson, Ohio. The stains were applied side-by-side to pressure treated pine by brush application. The stain of Example 6 showed greater penetration, and the stain appearances were comparable. However, the stain of Example 7 resulted in significant water beading, whereas the CWF-UV stain did not bead water substantially.

Examples 8 through 12 show reduced VOC emulsion compositions useful as wiping stain and glaze intermediates and stains and glazes.

Example 8. Example of Clear Water Based Glaze Utilizing

Aminoester and/or a substituted Alkanolamine for

Development of a 2.0 lbs/gal VOC Stain

	Item	% Weight

	2,2,4-Trimethyl-1,3-pentanediol	3.82
	diisobutyrate
	Aromatic 150	15.55
	Mineral Spirits 66/3	5.03
	Oxsol 100	4.51
	Irganox 1010	0.07
	Lubrizol OS #47550AF, 1X.5 LT	3.82

Heated to 100-110° F., mixed until dissolved, then added

Soy Salad Oil

2.26

Mixed, then added

Aerosil R972

1.21

Mixed 2-5 min, then added the following water slowly

DI Water

63.51

Then added

	Cycat 296-9	0.33
	Total	100.00
	Viscosity, RVDVE	142 cps
	pH	8.37
	Theoretical VOC	2.00 lbs/gal

Example 9. Example of Intermediate for Water Based Glaze/Wiping

Stain Utilizing Aminoester and/or a Substituted Alkanolamine

for Development of a 2.0 lbs/gal VOC Stain

	Item	% Weight

	Soy Salad Oil	21.67
	Aromatic 150	41.00
	Irganox 1010	0.67
	Lubrizol OS#47550AF	36.67

	Mixed until dissolved, with heating to
	100-110° F.

	Viscosity, #2 Zahn Signature cup, 77° F.	19-20 sec

Example 10. Example of Utilizing Intermediate of Example

9 for Development of Water-based Clear Glaze/Wiping Stain

	Item	% Weight

	Example 9	10.41
	Aerosil R972	1.21

Next, added

	Aromatic 150	11.17
	2,2,4-Trimethyl-1,3-pentanediol	3.82
	diisobutyrate
	Mineral Spirits 66/3	5.03
	Oxsol 100	4.51

Mixed thoroughly, then slowly added

DI Water

63.51

Mixed 10 to 15 minutes, then added

	Cycat 296-9	0.33
	Total	100.00
	Viscosity, RVDVE	142 cps
	Theoretical VOC	2.00 lbs/gal

Example 11. Example of Stain/Glaze Intermediate Base Incorporating

Aminoester and/or a substituted Alkanolamine for Development

of a 0.17 lbs VOC/lbs solids Stain

	Item	Wt %

	Aromatic 150	14.45
	Irganox 1010	0.29
	Oxsol 100	43.35
	Lubrizol OS#47550AF, 1X.5 LT	18.79
	Soy Salad Oil	23.12
	Total	100

Example 12. 0.17 lbs VOC/lbs solids Clear Stain

Item	Wt %

Example 11	23.52
DI Water	50.99
Nytal 300	10.20
Oxsol 100	15.30
Total	100
VOC, calculated	0.17 lbs VOC/lbs solids
Viscosity, #2 Zahn, signature cup, 77° F.	27 seconds

Preparation of oak and cherry panels utilizing tinted stains of Examples 10 and 12 as wiping stain/glaze resulted in panels with excellent color and clarity. The stains also wiped well and were brush blend able.

The clear stain of Example 8 was tinted per Example 13 below, and compared to Examples 14-19 for wipe ability, clean up, and finish clarity.

Example 13. Tinted Low VOC Wiping

Stain/Glaze Based on Example 8

	Item	Wt/grams

	Example 8	576.3
	Eagle Series 2000 WB1711 Burnt Umber	75

	Mixed

Example 14 (Comparative). Aqueous Stain/Glaze

Based on Joncryl 95 Vehicle

	Item	Wt/grams

	Joncryl 95	99.95
	Ethylene Glycol dibutyl ether	3
	Foamaster S	3
	Eagle Series 2000 WB1711 Burnt Umber	39.27
	Proxel GXL	0.5

	Mixed well until well blended; Premix the following 4
	items, then added under agitation

	Water	150.4
	Propylene Glycol	10.3
	Natrasol 250 HHBR PA	1
	Ammonia	0.34
	Total	305
	Viscosity, #2Zahn, 78 F., sec	16.2
	pH	8.02

Example 15 (Comparative). Aqueous Stain/Glaze

Based on Chemphol 821-3660 Vehicle

	Item	Wt/grams

	Chemphol 821-3660	99.95
	Surfynol 104 DPM	0.5
	Propylene Glycol	3
	Proxel GXL	0.5
	Water	50
	Eagle Series 2000 WB1711 Burnt Umber	39.27

	Mixed well until well blended; Premixed the following 4
	items, then added under agitation

	Water	100
	Natrasol 250 HHBR PA	1
	Ammonia	0.34
	Propylene Glycol	10.3
	Total	304.86
	Viscosity, #2Zahn, 77 F., sec	23
	pH	7.85

Chemphol 821-3660 is an aqueous alkyd dispersion designed for wood stains and paints manufactured by Cook Composite Polymers, Kansas City, Mo.

Example 16. Table 2. Formulation B (Laponite RDS Thickener

Solution) disclosed in Int'l Publ. No. WO 01/35719,

p. 20 (incorporated by reference herein)

	Item	Wt/grams

	Tap Water	45
	Laponite RDS	5

	Mixed until clear and uniform

Example 17. Table 1. Formulation A (CMCAB Dispersion)

disclosed in Int'l Publ. No. WO 01/35719, p.

19-20 (incorporated by reference herein)

	Item	Wt/grams

	Ethylene glycol butyl ether	563.8
	CMCAB 641.2	241.6

Mixed until dissolved, then added

	AMP-95	5.96
	DI Water	1188.6

Example 18. Table 3. Formulation C (CMCAB Stain)

disclosed in Int'l Publ. No. WO 01/35719, p.

20-21 (incorporated by reference herein)

	Item	Wt/grams

	DI Water	133
	Example 16, Formulation B	6.99
	SCT 275 Thickener	5.56

Mixed, then added

	Example 17, Formulation A	65.1
	(CMCAB Dispersion)

Mixed well, then added

	Eagle Series 2000 WB1711 Burnt Umber	39.27
	Propylene Glycol	50
	Total	300
	Viscosity, #2Zahn, 77 F., sec	17.38
	pH	6.88

Example 19, below is a stain of the invention based on Tergitol™ XD emulsifier. The stain has low VOC, good working properties, reduced grain raising compared to conventional aqueous stains, and can be utilized directly to wood as well as over washcoat.

Example 19. Aqueous Stain/Glaze Based on

Tergitol ™ XD Surfactant

	Item	Wt/grams

	2,2,4-Trimethyl-1,3-pentanediol	10
	diisobutyrate (TXIB)
	Solvesso 150	40
	Mineral Spirits 66/3 (Varsol)	15
	Parachlorobenzotrifluoride (Oxsol 100)	10
	Tergitol XD	10
	Irganox 1010	0.2

Heated to 100-110° F. to dissolve, then added under agitation

	Aerosil R972	3
	Soya Oil	6

	Heated the following water to 100° F. and added slowly
	with good agitation (1000-1500 rpm)

DI water

165

Mixed 10-15 minutes, then added

	Eagle Series 2000 WB1711 Burnt Umber	34
	DI water	7
	Total	300.2
	Viscosity, #2 Zahn, 77° F., sec	22.3
	pH	7.85

The compositions of Examples 13, 14, 15, 18, and 19 were evaluated in several different ways including panel development. Tables 2, 3, and 4 below compare various test results of the stains.

TABLE 2
Evaluation of Stains of Examples 13, 14, 15, 18, and 19

Stain

Test/Evaluation	Example 13	Example 18	Example 14	Example 19	Example 15
Wet Edge (0.5 g on	7 min, 5	6 min, 10	4 min, 23	10 minutes	6 min, 30
4X6 in glass plate)	seconds	seconds	seconds		seconds
Wet Edge (7 drops	10 minutes	10 minutes	5 min, 15	7 min, 12	4 min, 8
on 4X6 glass plate			seconds	seconds	seconds
and work in 4 in
square area)
Wet Edge (7 drops	2 min, 30	3 min, 3 sec;	1 min, 39	2 min;	2 min, 29
on 1.5X6 inch	seconds;	disappeared	seconds;	became	seconds;
ramin wood strip)	disappears	into wood;	became	sticky; very	became
	into wood -	somewhat	sticky; very	mottled	sticky; very
	smooth	mottled	mottled		mottled
Grain raising on	2	2	5	3	4
ramin wood (spray
and wipe)
(1 = good; 5 = bad)
Grain raising on	2	3	5	3	4
oak wood (spray
and wipe)
(1 = good; 5 = bad)
Washcoat attack	1	4 - sticky	4 - sticky	1	4 - sticky
(sprayed 12%
nitrocellulose
washcoat on ash
wood; dried for 30
min; sprayed
glaze/stain, let set
2 min, wiped clean)
(1 = no effect; 5 = bad)

TABLE 3
Evaluation of Stains of Examples 13, 14, 15, 18, and 19 - Cherry Panels
with toner, with and without washcoat; Acid cure sealer and topcoat
Sprayed wet coat wiping stain; flashed 5 min, wiped, brushed, and
hi-lited. Air Dried 1 hr, then 5 min @130° F.

Panel

1

2

3

4

5

Example	13	14	13	18	13	19	13	14	13	15
With Washcoat	N/A
Crosshatch			4B	4B	3B	3B-4B	4B	4B-5B	3B	3B
adhesion
Nickel scrape			6	9	7	9-10	5	8	5	6
adhesion (1 =
worse;
10 = best)
Wiping			Wiped	Wiped	Wiped	Wiped	Wiped	Wiped	Wiped	Wiped
			clean	clean	clean	clean	clean	clean	clean	clean
Color/clarity			Clean	Clean, but	Clean	Clean and	Clean	Clean and	Clean	Sl muddy
			and	not quite as	and	bright; sl	and	bright; v sl	and	and sl
			bright	clean and	bright	more grainy	bright	graininess	bright	grainy
				bright; sl		appearance
				more grainy
				appearance

Without Wash coat

Crosshatch	4B	4B	4B	4B	3B	4B	4B	4B	3B	3B
adhesion
Nickel scrape	6	7	6	8	7	8	5	9	5	6
adhesion
Wiping	wiped	Wiped	Wiped	Wiped	Wiped	Wiped	Wiped	Wiped	Wiped	Wiped
	clean	clean	clean	clean	clean	clean	clean	clean	clean	clean
Color/clarity	Clean	Clean,	Clean	Clean, but	Clean	Clean and	Clean	Clean and	Clean	Sl muddy
	and	sl	and	not quite as	and	bright; sl	and	bright; v sl	and	and sl
	bright	more	bright	clean and	bright	more grainy	bright	graininess	bright	grainy
		muddy		bright; sl		appearance
				more grainy
				appearance

TABLE 4
Evaluation of Stains of Examples 13, 14, 15, 18, and 19 - Cherry Panels
with toner, with and without washcoat; Acid cure sealer and topcoat
Sprayed wet coat wiping stain/glaze; flashed 5 min, break
down, set 10 min, wiped clean, cure @130° F.

Panel

6

7

8

9

10

Example	13	14	13	18	13	15	13	19	13	15

With Washcoat

Crosshatch	3B	3B	3B	4B-5B	3B	4B-5B	4B	5B	3B	4B
adhesion
Nickel scrape	5	9-10	6	10	6	7-8	5	8-9	6	6
adhesion
Wiping	Excellent	V.	Excellent	Streaky;	excellent	Did not	Wiped	Wiped	Wiped	V.
		Streaky;		did not		clean up,	clean	clean	clean	Streaky;
		did not		clean up		v streaky				did not
		clean up								clean up
Color/clarity	Clean	Muddy,	Clean	Muddy,	Clean	Muddy,	Clean	Clean	Clean	Muddy,
	and	removed	and	removed	and	removed	and	and	and	topcoat
	bright	WC;	bright	WC;	bright	WC	bright	bright	bright	lifts
		topcoat
		lifts

Without Wash coat

Crosshatch	3B	4B	3B	4B-5B	3B	4B	2B-3B	2B-3B	3B	3B
adhesion
Nickel scrape	4	9	4	9	5	9	2	5-6	5	8
adhesion
Wiping	wiped	Fair	Excellent	Sl	Wiped	Did not	Wiped	Wiped	Wiped	V.
	clean	clean		streaky	clean	clean up;	clean	clean	clean	Streaky;
		up				v streaky				did not
										clean up
Color/clarity	Clean	Muddy,	Clean	muddy	Clean	V muddy	Clean	Clean and	Clean	V muddy
	and	removed	and		and	and	and	bright;	and	and
	bright	WC;	bright		bright	topcoat	bright	v sl	bright	grainy
		topcoat				lifts		graininess
		lifts

Example 20, below illustrates a dispersion of water into a fluorocarbon modified acrylic polymer. The dispersion results in a reduced VOC fluorocarbon modified acrylic polymer useful for improving hydrophobicity and water and oil repellency of various substrates such as wood, composites, textiles, paper, and the like, and any substrate wherewith such improvements are useful.

Example 20. Aqueous Dispersion of Water

into a PerFluorinated Acrylic Polymer

	Item	Wt/grams

	Aromatic 150	23.84
	Lubrizol OS#47550AF	3.02

Mixed until dissolved, then added

Flexipel S-22 WS

20.27

Mixed well, then added under medium agitation

Tap water

57.00

	Product goes together very well; Very Foamy

The dispersion of Example 20 was applied to a Leneta chart with a 3 mil bird bar. A smooth uniform wet film resulted. After drying, the film was somewhat foamy, hazy, but not grainy, and slightly tacky. Application of water drops on the film resulted in significant water beading and splitting of the water drop into many drops. After the sample of Example 20 had sat for 13 days, the sample showed some separation, but stirred back in very easily and had minimal air present. A second draw down was made on a Leneta chart. A smooth white wet film resulted. The draw down was allowed to air dry overnight. A smooth, hazy, and slightly yellow film resulted that beads water. This latter drawdown was placed into an 80° C. oven for 25 minutes. A clear, glossy, slightly yellow, and slightly tacky film resulted. The oven-aged sample beaded water significantly better than the non-oven-aged sample.

Illustrative applications for this technology include exterior siding that is water resistant, textiles and nonwovens, house paint that resists water and stains, decks and porches, rain wear and umbrellas, and shoes.

Example 21

Water-in-Oil Dispersions Containing Waxes

The inventive dispersions incorporating a wax may be used in such applications as, but not limited to, edge seal coatings, wax additives, lubricants, and wax coatings. The wax dispersion formulation is shown below in Table 5 (see Example 20 for the base formula).

TABLE 5
Addition of Wax to Water in Oil Dispersion

Item (g)	Weight (g)	Weight (%)

Solvesso 150	31.46	11.44
Mineral Spirits	31.46	11.44
Paraffin Wax R2531	53.54	19.47
Lubrizol OS #47550AF	7.98	2.90

Mixed with heat to dissolve, then added with medium agitation:

Distilled Water	150.56	54.74
TOTAL	275.00	100.00

% NVM	22.37
% Wax	19.47

Viscosity, Brookfield RV DV-E,	1100 cps @ 11.0% T
sp#6, 100 rpm, @ 78 F.

Next a resin was added as shown below in Table 6.

TABLE 6
Addition of Resin

	Item	Weight (g)

	Composition of Table 5	100.00
	UROTUF F-19-M50	10.00
	TOTAL	110.00
	NVM	24.88%
	Wax	17.70%

A competitive wax coating, shown below in Table 7, was made to compare with the properties of the coating of Table 6.

TABLE 7
Competitive Wax Coating

	Item (g)	Weight (g)

	Slip Ayd SL 145E	21.64
	40% EB-49	6.25
	Tap Water	27.12
	TOTAL	55.01
	NVM	22.25%
	Wax	17.70%

The samples were evaluated for film formation and appearance by a 1.5 mil DD on Leneta Form 7B. The results are detailed below in Table 8.

TABLE 8
Comparison of Coatings of Tables 6 and
7 - 1.5 mil DD on Leneta Form 7B

Cure Schedule	Coating of Table 6	Coating of Table 7
Air dry	did not form a film, has	formed a film, puddled
	large wax particles	in center and right edge
Flash completely,	formed a film, puddled	formed a film, puddled
20′@80° C., cool	on right edge	in center and top edge
overnight

Two 20 RDS DDs on masonite board were performed for each sample. One sample air dried overnight and the other air dried to flash, put in an 80° C. oven for 20 minutes, and then cooled overnight. These results are detailed below in Table 9.

TABLE 9
Comparison of Coatings of Tables 6
and 7 - 20RDS DD on Masonite Board

Cure Schedule	Coating of Table 6	Coating of Table 7
Air dried	did not form a film, has	formed a film, splotchy,
	large wax particles	wax flowed to the top
Flashed completely,	formed a film, smooth	formed a film, splotchy,
20′@80° C., cooled	and even appearance	wax flowed to the top
overnight

Next, to keep the wax in the dispersion, the formulation of Table 5 was remade keeping the batch warm while mixing. This formula is shown below in Table 10.

TABLE 10
Formulation

	Item	Weight (g)

	Solvesso 150	15.73
	Mineral Spirits 66/3	15.73
	Paraffin Wax R2531	26.77
	Lubrizol OS#47550AF	3.99

	Mixed with heat to dissolve, continued heating and
	mixing then added:

	DI Water	75.28
	TOTAL	137.50

Next a resin was added to the formulation of Table 10, as shown below in Table 11.

TABLE 11
Formulation

	Item	Weight (g)

	Formul. of Table 10	50.00
	UROTUF F-19-M-50	5.00
	TOTAL	55.00
	NVM	24.88%
	Wax	17.70%

A 20 RDS DD was performed on the masonite board and then put immediately in the oven for 20 minutes @ 80° C. It formed a film, and although it appeared splotchy it felt smooth. A 1.5 mil DD was performed on Leneta Form7B and was allowed to air dry overnight. This DD did not form a film and had large wax particles in it. It appears that the sample remains uniform when heated, but when it cools the wax particles come out of the dispersion.

All of the samples were tested for water resistance by performing the Cobb Water Soak Test on the drawdowns made on masonite board. The steps to the test are: 1) Drill ½ in. hole in masonite board; 2) Use 180 grit sandpaper to clean holes and sand edges around holes; 3) Weigh board; 4) Place gasket next to coated side of board; 5) Tighten nuts with 9/16 in. wrench; 6) Pour 100 mL in circle and cover, 7) After 4 hours remove water from board and blot dry; and 8) Reweigh board.

The results of the tests are detailed below in Table 12.

TABLE 12
Cobb Water Soak Test Results (DD on Masonite Board)

Sample		Wt (g)	Wt (g)	After −	% Wt
Coating	DD Cure Schedule	before	after	Before (g)	increase

Table 7	flash, 20′@80° C.,	254.31	255.48	1.17	0.46
	cool O.N.
Table 6	flash, 20′@80° C.,	258.80	259.98	1.18	0.46
	cool O.N.
Blank	None	254.15	254.95	0.80	0.32
Table 11	20′@80° C.,	259.14	259.98	0.84	0.32
	cool O.N.
Table 6	Air dry overnight	266.02	266.76	0.74	0.28
Blank	None	252.62	253.44	0.82	0.32
Table 7	Air dry overnight	262.34	263.14	0.80	0.30
Blank	20′@80° C.,	254.36	256.24	1.88	0.73
	cool O.N.

Water resistance was evaluated again by a 20RDS DD on a 7×7 MDF panel. The drawdowns were placed in an 80° C. oven for 20 minutes and then cooled overnight. The same procedure was followed as stated above, except the test was left on for 24 hours. The results are shown below in Table 13.

TABLE 13
Cobb Water Soak Test Results (DD on MDF Panel)

	Wt (g)	Wt (g)	After −	% Wt
Sample Coating	before	after	Before (g)	increase

Blank	304.76	314.75	9.99	3.28
Table 11	296.64	306.11	9.47	3.19
Example 20	345.39	348.60	3.21	0.93
Table 7	324.96	329.61	4.65	1.43

The wax dispersion must be kept warm while mixing for the wax particles to stay in solution. Wax dispersions of Tables 6 and 11 performed equally to the SlipAyd formulation, Table 7 in terms of water resistance on the masonite board. However when the water soak test was applied to the MDF panel for 24 hours, the coating of Table 11 absorbed more water than the coating of Table 7.

Example 22

Water-in-Oil Dispersions Containing Silicones

The inventive dispersions incorporating silicones may be used in such applications as, but not limited to personal care items, car and furniture polishes, tire wet products, release agents, flow and leveling agents, antifoams, and concrete treatments.

A silicone fluid was added to the water-in-oil dispersion of the base formula of Example 20 as shown below in Table 14.

TABLE 14
Addition of Silicone to Water in Oil Dispersion

	Item	Weight (g)	Weight (%)

	Mineral Spirits 66/3	17.16	11.44
	SF-69	46.38	30.92
	Lubrizol OS#47550AF	4.35	2.90

Mixed well, then added with medium agitation

	Distilled Water	82.11	54.74
	TOTAL	150.00	100.00

A liquid layer formed on top of the sample, which appeared to have coagulated. Mineral spirits was replaced with xylene, to see if the SF-69 would be soluble in it. This formula is shown below in Table 15.

TABLE 15
Dispersion of Table 14 with Xylene in place of Mineral Spirits

	Item	Weight (g)	Weight (%)

	Xylene	17.16	11.44
	SF-69	46.38	30.92
	Lubrizol OS#47550AF	4.35	2.90

Mixed well, then added with medium agitation

	Distilled Water	82.11	54.74
	TOTAL	150.00	100.00

This sample also coagulated and separated. Approximately 1.03 g more of OS#47550AF was added to try to make the sample smooth and uniform. However, the sample remained coagulated. Next, the amount of silicone was cut in half and replaced with xylene. This formulation is shown below in Table 16.

TABLE 16
Formulation with Reduced Silicone and Xylene Added

	Item	Weight (g)	Weight (%)

	Mineral Spirits	17.16	14.00
	Xylene	23.19	18.91
	SF-69	23.19	18.91
	Lubrizol OS#47550AF	4.35	3.55

Mixed well, then added with medium agitation

	Distilled Water	54.74	44.63
	TOTAL	122.63	100.00

This formula had little separation and no coagulation. Next, the above formula was made with DC200 in place of SF-69 as shown in Table 17.

TABLE 17
Formulation with DC200

	Item	Weight (g)	Weight (%)

	Mineral Spirits	17.16	14.00
	Xylene	23.19	18.91
	DC 200	23.19	18.91
	Lubrizol OS#47550AF	4.35	3.55

Mixed well, then added with medium agitation

	Distilled Water	54.74	44.63
	TOTAL	122.63	100.00

The two samples of Tables 16 and 17 were evaluated for polishing. Both samples polished the polishing panel, beaded water, and had slight improvement in mar resistance in comparison to the product on the polishing panel. Both samples were approximately equal in appearance, although it seemed that the Table 16 composition took more effort to rub in than the Table 17 composition.

Next, the samples were evaluated as defoamers in a water based acrylic dispersion coating based on AC 2538 polymer from Alberdingk Boley, Greensboro, N.C., with FC-129 added for foaming. That formulation is described in Table 18. The samples were agitated @1200 rpm for 5 minutes then poured into a tared 100 mL cylinder. The foam height of each sample was measured initially and after 10 minutes, along with the portion of the sample without foam. The results are shown below in Table 19.

TABLE 18
Aqueous Acrylic Coating for Evaluation of Defoaming Efficacy

	Item	Wt/grams

	Tap water	723.10
	Diethylene glycol butyl ether	29.58
	AC 2538 polymer	1238.18
	RM2020	14.76

TABLE 19
Evaluation of Silicone Dispersions as Defoamers

	Item	Weight (g)

	Table 18 Coating	45.00	45.00	45.00
	FC-129	0.27	0.26	0.26
	Formul. of Table 16	—	0.20	—
	Formul. of Table 17	—	—	0.20
	Total Ht coating and foam	139 mm	133 mm	125 mm
	after 10′
	Bottom liquid Ht (part w/o	22 mm	46 mm	50 mm
	foam) after 10′
	Foam Reduction (or	16	35	40
	deareation) (%)

Silicones can be added to the water-in-oil dispersion. Although there is some separation, the samples mix back together easily. Both samples give good results for polishing, mar resistance, and defoaming.

Example 23

Water-in-Oil Dispersions Containing Chlorinated Polymers

The inventive dispersions incorporating chlorinated polymers may be used in such applications as, but not limited to adhesion promoter coatings for plastic.

Chlorinated Polyolefin (CP) 343-4 was added to the water-in-oil dispersion of the base formula of Example 20 as shown below in Table 20.

TABLE 20
Addition of Chlorinated Polyolefin to Water in Oil Dispersion

	Item	Weight (g)	Weight (%)

	Solvesso 100	34.34	22.89
	CP 343-4	29.20	19.47

Mixed until dissolved, then added:

Lubrizol OS#47550AF

4.35

2.90

Mixed and added with medium agitation:

	Distilled Water	82.11	54.74
	TOTAL	150.00	100.00

	Viscosity, Brookfield RV-DVE,	420 cps @ 4.2% T
	sp#6, 100 rpm, @78° F.

Next a polyurethane resin was added to the formulation of Table 19 as shown below in Table 21.

TABLE 21
Addition of Resin

	Item	Weight (g)

	Formulation of Table 20	75.00
	UROTUF F19-M-50	7.50
	TOTAL	82.50

A 1.5 mil DD of each sample was made on Leneta Form 7B and allowed to air dry overnight to evaluate appearance. The formulation of Table 20 formed a yellowish film that cratered. The formulation of Table 21 formed a smooth yellowish film.

Next the samples were sprayed on TPO Engineered Test Plaques and cured by 30′ flash, 10′ @ 66° C., then 1 hr cool. The samples had not flashed completely before they were placed in the oven; this caused the formulation of Table 21 to blister. The samples were re-sprayed on TPO and flashed for 2 hours, 1 hr @66° C., and cooled overnight.

A 2K urethane coating was made to apply to the coated TPO plaques and a blank TPO plaque. This formulation is shown below in Table 22.

TABLE 22
2K Urethane Coating

	Item	Volume (oz.)
	NAPA Acrylic Urethane Enamel	3
	MSU 475 Hardener	1

After the plaques were sprayed, they air-dried for 7 days and then were evaluated for adhesion using ASTM D3359—tape cross hatch adhesion test. The results are detailed below in Table 23.

TABLE 23
Evaluation of Adhesion on TPO Plaques

	Sample	Results
	Formul. of Table 19	0% removed, 5B
	Formul. of Table 20	0% removed, 5B
	Blank	0% removed, 5B, but 100%
		removed on edge of panel

Next, the plaques were placed in a water bath in which the bottom half of the plaques soaked for 10 days. The plaques were then removed, blotted dry, allowed to recover for 1 hour, and then evaluated for adhesion and blistering. These results are detailed below in Table 24.

TABLE 24
Evaluation of Adhesion on Water Soaked TPO Plaques

Sample	Water Soak Results	Non-soaked Results
Formul. of Table 20	orange peel	orange peel
	0% removed, 5B	0% removed, 5B
Formul. of Table 21	0% removed, 5B	0% removed, 5B
Blank	blisters	slight blisters
	failed on cutting, 0B	0% removed, 5B

Chlorinated polyolefin can be added to the water-in-oil dispersion, giving good adhesion results.

Further, it is believed that the addition of the chlorinated polyolefin to the system improves the ability to disperse and maintain dispersion stability. Thus, a UV curable dispersion has been made that is coated onto TPO, cured, and can be subsequently coated and have excellent adhesion. Example 24, below illustrates this property.

Example 24

Dispersions for Coating TPO Plastic, Including UV Curable Dispersions

TABLE 25
UV Monomer-Photoinitiator Blend

	Item	Wt/grams

	Sartomer SR344	2478.0
	TMPTA-N	1006.69
	Irgacure 184	329.11
	Tego Wet 500	29.03

TABLE 26
UV Coating

	Item	Wt/grams

	Formulation of Table 25	76.42
	Ebecryl 3212 epoxy acrylate oligomer	123.58

TABLE 27
Emulsified Water Utilizing Chlorinated Polyolefin

	Item	Wt/grams

	Solvesso 100	57.23
	Chlorinated Polyolefin CP 343-3	48.67

Mixed until dissolved, then added

Lubrizol OS#47550AF

7.38

Mixed and added the following with medium agitation

	DI water	136.85

TABLE 28
Formulations Utilizing Emulsified Water

Formulation, Wt/grams

Item	A	B

Formul. of Table 27	75	75
Urotuf F-19-M-50	7.50
Formul. of Table 26		7.5
Result	Smooth dispersion	Smooth dispersion

Formulation B was spray applied to a piece of TPO that had been wiped with isopropanol. The coated TPO plaque was allowed to air flash for 20 minutes, and then was cured for 25 minutes in an oven set at 49° C. with its doors open. The coated and oven cured plaque was then cured by UV exposure (American Ultraviolet curing unit, Hg lamp housed in an elliptical reflector, at 300 watts; 1 pass, at 30 feet per minute, resulting in 304 mj/m², 0.674 w/cm² cure energy UVA). The UV cured panel was then coated with a Napa 2K acrylic urethane refinish topcoat. The panel was allowed to sit 18 days at room temperature and then the adhesion evaluated by ASTM 3359—results—5B (Excellent). The coated and cured plaque was then exposed to a water bath for 10 days. The plaque was removed and blotted dry. There was no sign of blistering. The plaque was allowed to recover for 1 hour and the adhesion re-evaluated by ASTM 3359 on the water exposed area—result—5B (Excellent).

It is also noted that the water exposed and wiped panel has slight less gloss, slight textured surface and appears to be slight less white (i.e., more yellow).

Example 25

Dual Emulsions

A dual emulsion has been prepared, utilizing a chlorinated polyolefin as a hydrophobic moiety and Alberdingk H595 (Alberdingk Boley, Inc., Greensboro, N.C.), an aqueous acrylate-styrene copolymer dispersion, instead of water. The formulation is described below.

TABLE 29
Formulation Incorporating Alberdingk H595 Aqueous Polymer
In Place of Water in Formulation of Table 26

Item	Wt/grams

Solvesso 100	57.23
CP-343-3	48.73

Mixed until dissolved, then added

Lubrizol OS#47550AF

7.54

Mixed until dissolved, then added

Alberdingk H595

136.90

Product goes together fine, but thickened tremendously

Mineral Spirits 66/3

40.20

Addition of mineral spirits 66/3 lowered viscosity very significantly

and product looks very uniform. Product remained uniform for greater

than 1 month

Made 6 mil DD on form 7B paper, air	Film is clear but has a yellow
dry over weekend	tint over white portion. Film
	is slightly tacky and soft
Made 6 mil DD on plate glass, air dry	Film has a yellow cast, but
over weekend	clear. Film can be stripped
	from the glass

The formulation of Table 29 was applied to treated pine decking. The product appears to brush well, and has a good appearance. The formulation was tinted with alkyd tint colors from Elementis Specialties (Tint-AYD AL series). The product results in a very clear colored finish, but did not brush as well as expected.

Example 26

Aqueous Deck Stain Formulation

Example 26 illustrates an aqueous deck stain formulation using ethanoldiethonium polyisobutenyl triethylaminosuccinate as an emulsifier.

Example 26. Preparation of an Aqueous Deck Stain

Formulation Containing Chemccinate 5603

	Item

	Solvesso 150	16
	Paraffin Wax R2531	2.7
	Chemron Chemccinate 5603	8.2
	Irganox 1010	0.27

Heated to 100-110° F.

	Foamtrol 110	4.1
	PolyFox PF3320	1.15
	Urotuff 19M50	54.8
	Michem Wax 433	1.36
	Hombitec RM401LP	9.6
	Tinuvin CGL1130	0.68
	Busan 1105	2.7
	Solvesso 150	48.4
	Mineral Spirits	23.36

Added slowly under agitation

Water

206.25

Tinted with

	Tint-AYD AL600	4.1
	Tint-AYD AL499	6.84

Premixed the next two items and added

	Solvesso 150	6.44
	BYK 333	2.75
	Appearance	Smooth, uniform (equal)
	Viscosity, #2Zahn, signature cup, sec	27.3, 27.4
	Color	Reddish orange (equal)
	Brushability	Good (equal)
	Water bead test	Good (equal)

The following examples show polyols useful in coatings of the invention.

Example 27

Hydroxy-Functional Acrylic Resin Coating Formulation

To a mixing vessel equipped with a cowles blade was charged about 11 grams of methyl n-amyl ketone, about 34 grams of Solvesso 150, about 40 grams of a hydroxyl functional acrylic resin having a molecular weight of 20,000, acid number of 10, and hydroxyl equivalent weight of 650, and about 6 grams of Lubrizol OS#47550 AF. This mixture was mixed well. Then about 110 grams of deionized water was added to the mixture with medium agitation. A water-in-acrylic resin emulsion was obtained having a viscosity (78° F., Brookfield RV DVE, sp6, 100 rpm) of about 2320 cps.

Example 28

Unsaturated Polyester Resin Coating Formulation

To a mixing vessel equipped with a cowles blade was charged about 15 grams of methyl n-amyl ketone, about 41 grams of Solvesso 150, about 30 grams of an unsaturated polyester resin having a molecular weight of about 950, an acid number of about 25, and an iodine number of about 70, and about 6 grams of Lubrizol OS#47550 AF.

This mixture was mixed well. Then about 110 grams of deionized water was added to the mixture with medium agitation. A water-in-modified unsaturated polyester resin emulsion was obtained having a viscosity (78° F., Brookfield RV DVE, sp6, 100 rpm) of about 470 cps.

Example 29

Caprolactone Polyol Formulation

A 60% solids solution of CAPA2047A Caprolactone polyol was made by charging 20 grams methyl propyl ketone, 20 grams xylene, and 60 grams CAPA 2047A caprolactone polyol (Solvay Caprolactones, Warrington, England) to a mixing vessel equipped with a cowles dissolver and mixing until solution was obtained.

Example 30

Aqueous Caprolactone-Based Polyol Coating Formulation

To a mixing vessel equipped with a cowles blade was charged about 11 grams of methyl n-amyl ketone, about 34 grams of Solvesso 150, about 40 grams of the formulation of Example 29, and about 6 grams of Lubrizol OS#47550 AF. This mixture was mixed well. Then about 110 grams of deionized water was added to the mixture with medium agitation. A water-in-caprolactone-based polyol resin emulsion was obtained having a viscosity (78° F., Brookfield RV DVE, sp6, 100 rpm) of about 510 cps.

Example 31

Polybutadiene Polyol Coating Formulation

To a mixing vessel equipped with a cowles blade was charged about 17 grams of methyl n-amyl ketone, about 45 grams of Solvesso 150, about 23 grams Polybd R-20LM (Sartomer Company, Exton, Pa.), and about 6 grams of Lubrizol OS#47550 AF. This mixture was mixed well. Then about 110 grams of deionized water was added to the mixture with medium agitation. A water-in-polybutadiene polyol resin emulsion was obtained having a viscosity (78° F., Brookfield RV DVE, sp6, 100 rpm) of about 1140 cps.

The formulations of Examples 27, 28, 30 and 31 all went together well forming a smooth dispersion. After several weeks, the samples showed separation. All samples were crosslinked with polyisocyanates and evaluated for chemical resistance after 7 day aging of a 1.5 mil wet film drawdown. The following table details the crosslinked samples and the results obtained.

TABLE 30
Detail of Crosslinked Samples and Results Obtained

Example

Item	27	27	28	28	30	30	31	31

Example 27(g)	20	20
Example 28(g)			20	20
Example 30(g)					20	20
Example 31(g)							20	20
Desmodur	3.5		3.5		3.5		3.5
N3300(g)
Bayhydur VP		3.5		3.5		3.5		3.5
LS 2336(g)
					Jell	Jell	Jell	Jell
Red marker	0.67	2.71	4.81	1.29	N/A	N/A	N/A	N/A
resistance Δa
1 hr mustard	2.0	9.28	13.59	23.60	N/A	N/A	N/A	N/A
stain resistance
Δb
24 hr detergent	No effect	Hazy	Sticky	sticky	N/A	N/A	N/A	N/A
resistance
24 hour ethanol	No visual	Hazy	Sticky	Hazy	N/A	N/A	N/A	N/A
resistance	effect			sticky
24 hour MEK	Lifted,	Lifted,	Sticky,	Sticky,	N/A	N/A	N/A	N/A
spot resistance	sticky	sticky, tore	tore	tore
		through
		paper

The following examples show that finished coating formulations may be useful with the invention for reduction of VOCs.

Example 32

2K Solvent-Based Acrylic Coating

To a mixing vessel equipped with an agitator blade, about 35% by weight of a ketone solvent blend was added. To this solvent blend was added 0.042% by weight of a 10% (wt) solution of dibutyl tin dilaurate catalyst and 2.3% by weight UV absorber. Finally, a blend of polyols (comprising 42.8% acrylic polyol Acrylamac 232-1700 available from Resolution Technologies, Carpentersville, Ill., and 15.5% of an acrylic polyol having a number average molecular weight of about 1900, a polydispersibility of about 2.5, and a hydroxyl number of about 130, and a cellulose acetate butyrate polyol having a number average molecular weight of about 30,000, a butyryl content of about 52%, an acetyl content of about 2% and a hydroxyl content of about 1.8%) were added. The blend was agitated until dissolved.

Example 33 shows the incorporation of water into the coating of Example 32, while Examples 34 and 35 compare crosslinking of the standard solvent-based coating to the water-incorporated coating dispersion.

Example 33

Aqueous 2K Acrylic Coating

About 42 grams of the composition of Example 32 and about 3 grams of Lubrizol OS#47550AF were mixed well. About 55 grams of deionized water was added with medium agitation, resulting in an emulsion having a non-volatile volume of 21.17%. The sample dispersed fine, showed slight separation, but mixed back together well.

Example 34

Crosslinked Acrylic Solvent-Based Coating

About 5.6 grams of the crosslinker Desmodur N3300 was added to 44.4 grams of the composition of Example 32 and mixed well. The non-volatile volume was 46.86%.

Example 35

Cross-Linked Aqueous Acrylic Coating

About 1.8 grams of Desmodur N3300 was added to 33.33 grams of the composition of Example 33 with medium agitation. The non-volatile volume was 24.53%.

A 1.5 mil drawdown was made on Leneta Form 7B with Examples 33 and 35, while a 3 mil drawdown was made on Leneta Form 7B with Examples 34 and 36. The films were allowed to air dry 7 days and then evaluated for stain and solvent resistance. The results are detailed in the following table.

TABLE 31
Stain and Chemical Resistance Results
of Films Obtained From Examples 32-35

Example	32	33	34	35

Red Marker	44.85	34.64	3.0	8.32
Resistance, Δa
1 hr Mustard	17	15.61	11.82	13.29
Resistance, Δb
24 hr Detergent	Hazy	Hazy	No effect	Hazy
Resistance
24 hr Ethanol	Lifted,	Lifted,	No effect	Hazy
Resistance	tore paper	coating removed
24 hr MEK	Lifted,	Lifted;	Lifted,	Lifted,
Resistance	tore paper	tore paper	tore paper	tore paper

Example 36, below is a nitrocellulose lacquer formulation, while Example 37 is a formulation showing the dispersion of water into the lacquer.

Example 36

Nitrocellulose Lacquer Formulation

To a mixing vessel equipped with an agitator blade was charged about 10% by weight of an alkyd solution of a mixture of castor and sunflower alkyds, about 9% by weight of a mixture of ½ second and ¼ second nitrocellulose wet with isopropanol, about 2.5% by weight diisonyl phthalate, and about 78% by weight organic solvent. The lacquer was mixed until a uniform, clear solution was obtained.

Example 37

Aqueous Nitrocellulose Lacquer Formulation

About 3 grams of Lubrizol OS#47550AF was added to about 42 grams of the lacquer formulation of Example 36, and mixed well. Then, about 55 grams of deionized water was added with medium agitation. The viscosity (at 80° F., #2 Zahn, signature cup) was 15.53 sec and the non-volatile volume was 7.64%.

The aqueous formulation went together well, and was stable for about 1 month. The sample also did not form a uniform film. Improvements are expected with the use of slower evaporating, more hydrophobic solvent combinations.

Example 38, below displays an acid cure coating formulation, and Example 39 gives an example of incorporating water into the Example 38 formulation.

Example 38

Acid-Cure Coating Intermediate Formulation

To a mixing vessel equipped with an agitator blade, was added 39.83% by weight of a solvent mixture of esters, ketones, and aromatic hydrocarbons. To this mixture was added 21.18% by weight of a mixture of primary alcohols and 2.85% of a hydroxyl modified vinyl chloride/vinyl acetate polymer having a vinyl chloride content of about 81%, a vinyl acetate content of about 4%, a hydroxylalkyl acrylate content of about 15% with a hydroxyl value of about 66 and a number average molecular weight of about 15000; and 2.85% of a cellulose acetate butyrate polyol having a number average molecular weight of about 30,000, a butyryl content of about 52%, an acetyl content of about 2% and a hydroxyl content of about 1.8%. The blend was mixed until the hydroxyl functional copolymer polyol was dissolved, and then 15.22% by weight of a coconut alkyd was added, followed by 18.07% by weight of a blend of aminoplast crosslinkers of urea-formaldehyde and melamine formaldehyde. The blend was mixed until uniform and clear.

Example 39

Aqueous Acid-Cure Formulation

About 3 grams of Lubrizol OS#47550AF and 42.35 grams of the formulation of Example 38 was mixed well. About 55 grams of deionized water was then added with medium agitation. The non-volatile volume was 12.72%.

The formulation of Example 39 went together well and remained stable except for a slight separation that could easily be restirred. The sample of Example 39 was catalyzed with 0.94% (wt) para-toluene sulfonic acid and a film applied with a 30 RDS draw down bar. The resultant coating cured to a soft, slightly yellow film upon air dry.

Example 40 shows a CAB/Acrylic coating formulation. Example 41 is an example of incorporating water into the Example 40 formulation.

Example 40. CAB/Acrylic Coating

	Item	Wt/grams

	Toluene	28
	VM&P Naphtha	36
	CAB 551.2	40
	Paraloid B-66	28
	Butyl Acetate	36
	Methyl ethyl ketone	30
	Butanol	44
	Methyl n-amyl ketone	92
	Ethanol (Duplicating Fluid 5/95)	49
	Santicizer 160	12
	SF-69 (1% in Xylene)	2.00
	Total	397
	Non-Volatile Volume	15.32%

Example 41. Dispersion of Water into Example 40

	Item	Wt/grams

	Example 40	42.35
	Lubrizol OS#47550AF	2.90

Mixed well, then added with medium agitation

	DI water	54.74
	Total	99.99
	Non-volatile volume	9.89%

Example 41 went together well. A 30 RDS draw down resulted in incomplete film formation.

The following examples show how water can be emulsified directly, with subsequent addition of various coatings such as UV coatings, and show how the addition of chlorinated polyolefin (CPO) helps improve incorporation of such items and improve cure of UV curable formulations.

Example 42 displays an emulsified water sample. Example 43 displays a UV curable coating, and Example 44 shows how the UV curable coating may be added to the emulsified water Example 42. Examples 45 and 46 show the results of emulsifying water directly into the UV cure coating.

Example 42 - Emulsified Water

	Item	Wt/grams

	Solvesso 100	28.62
	Xylene	24.34
	Lubrizol OS# 47550AF	3.63

Mixed well, then added with medium agitation

	DI water	68.43
	Total	125.02
	Viscosity @80 F., #2Zahn, signature cup	14.09 sec

Example 43 - UV Coating

	Item	Wt/grams

	Sartomer SR 344	49.28
	TMPTA-N	20.02
	Irgacure 184	6.54
	TegoWet 500	0.58
	Astrocure 78	123.58

Example 44 - Formulation Incorporating

Example 44 into Example 43

	Item	Wt/grams

	Example 42	30
	Example 43	3
	Total	33

	Goes together well

Example 45 - Comparison Formulation Showing

Incorporation of Water into UV Coating

	Item	Wt/grams

	DPGDA	21.36
	TMPTA	10.68
	Irgacure 184	3.01
	Astrocure 78	43.27
	Lubrizol OS#47550AF	4.06

Mixed well, then added with medium agitation

	DI water	76.64
	Total	159.03
	The sample appeared to have stayed together initially after the water was added, but after mixing for 10 minutes, the dispersion separated with a sponge-like appearance.

Example 46 - Comparison Formulation Showing

Incorporation of Water into UV Coating

	Item	Wt/grams

	Solvesso 150	10.68
	Methyl n-amyl ketone	10.68
	TMPTA	10.68
	Irgacure 184	2.16
	Astrocure 78	43.27
	Lubrizol OS#47550AF	4.06

Mixed well, then added with medium agitation

	DI water	76.64
	Total	158.17
	The sample started jelling after 37 grams of water was added and completely jelled after 55 grams of water.

Example 47 shows a UV curable coating formulation and Example 48 shows the incorporation of Example 47 into Example 42.

Example 47 - UV Curable Coating

	Item	Wt/grams

	Sartomer SR 344	49.28
	TMPTA-N	20.02
	Irgacure 184	6.54
	TegoWet 500	0.58
	Ebecryl 3212	123.58

Example 48 - Formulation Incorporating

Example 47 into Example 42

	Item	Wt/grams

	Example 42	30
	Example 47	3
	Total	33

	Goes together well

The coating of Example 48 was compared to the coating of Example 24, Table 28—B which utilized CPO to make the emulsified water. The samples were applied to Leneta Form N2A with a 20 RDS Rod. The samples were allowed to air flash overnight, and were exposed to 1 hr force dry at 66° C., then were UV cured at 604 mj/cm2 with a medium pressure Hg vapor lamp. The coating of Example 24, Table 28—B produced a more uniform drawdown appearance both after air flash, oven dry, and UV cure. It also cured to a tack free film within 5 seconds out of the UV unit whereas the coating of Example 48 did not cure. Microscopic analysis shows that emulsification of water in the presence of CPO results in improved dispersion uniformity and cure.

Examples 49-51 describe an aqueous primer composition of the invention.

Example 49

Water-Based Pigment Dispersion

To a stainless steel mixing vessel was charged 19.80 grams tap water, 8.80 grams Disperbyk 190, 1.0 grams BYK-024, both from BYK-Chemie USA (Wallingford, Conn.), and 0.10 grams Proxel GXL, available from Zeneca Biocides, (Wilmington, Del.). The following was added under agitation: 0.30 grams fumed silica, 18.80 grams aluminum silicate, 13.71 grams Titanium dioxide, and 37.70 grams sodium potassium alumino silicate. The mixture was then mixed at high speed with a dispersing blade to a grind of N.S. 5½-7 as measured on a hegman gage. A pasty, medium viscosity dispersion results.

Example 50

Organic Phase Composition

To a stainless steel mixing vessel was charged 100 grams of a 75% solids solution of a medium-Soya alkyd resin, 27.72 grams of a vegetable oil having an iodine value of 120-141 and a saponification value of 180-200, and 5.75 grams of a low molecular weight amine coupled polyisobutylene succan derivative. The blend was mixed for 15 minutes at 100-110 degrees F.

Example 51

Aqueous Primer Composition

To a stainless steel mixing vessel was charged 40 grams of the composition of Example 50. To this was added 0.19 grams Nuocure CK 10%, 0.94 grams Nuocure calcium 6%, 0.92 grams Nuocure Zr 12%, all three available from Elementis (East Saint Laths, Ill.). The components were mixed well, and then 182.75 grams of the composition of Example 49 was added under agitation. The mixture was mixed for 10-15 minutes and then 26.12 grams of tap water was added and mixed for another 15 minutes.

A smooth white primer with a VOC of less than 100 g/l resulted with a viscosity of 1550 cps at 50 rpm as determined on a Brookfield viscometer with a #6 spindle. The sample was found to be stable for 7 days at 49° C., pass 5 freeze thaw cycles, have good dry and biding properties, and good adhesion.

Table 32 provides a description of various products used in the Examples described above.

TABLE 32
Description of Products in Examples

Item	Supplier	Composition
Solvent 150	Exxon Mobil	Aromatic containing petroleum hydrocarbon
	Houston TX
Paraffin wax R	Moore and Munger	Fully refined paraffin wax - petroleum hydrocarbons
2531	Shelton, CT
Lubrizol 47550AF	Lubrizol	low molecular weight amine coupled PBU
	Wickliffe, OH	[Polyisobutylene] succan derivative and is oil free,
		i.e. ethanoldiethonium polyisobutenyl
		triethylaminosuccinate
Irganox 1010	Ciba	Tetrakis[methylene(3,5-ditert-butyl-4-hydroxyhydro
	Tarrytown, NY	cinnamate)methane
Foamtrol 110	Ultra Additives	Organosiloxane polymer defoamer
	Paterson, NJ
PolyFox PF3320	Omnova Solutions	Fluorinated oxetane oligomer
	Akron, OH
Urotuff 19M50	Reichhold	Oil-modified polyurethane resin
	Durham, NC
Busan 1105	Buckman	10% (2-Thiocyanomethythio)benzothiazole and 10%
	Laboratories	Methylene bis(thiocyanate)
	Memphis, TN
Tinuvin 1130	Ciba	UV absorber
	Tarrytown, NY
Michelman 433	Michelman Inc	Carnauba wax
	Cincinnati, OH
Hombitec RM	Sachtleben Chemie	Nano Titanium dioxide dispersion
401LP	New York, NY
Tint-AYD AL600	Elementis Specialties	Transparent red oxide pigment dispersion in alkyd
	Hightstown, NJ	resin
Tint-AYD AL499	Elementis Specialties	Transparent yellow oxide pigment dispersion in
	Hightstown, NJ	alkyd resin
CAPA 2047A	Solvay	2-oxepanone, polymer with 1,6-hexanediol
	Warrington, Cheshire
	WA4 6HB
Polybd R-20LM	Sartomer	1,3-butadiene, homopolymer, hydroxy terminated
resin	Exton, PA
MetaCure T-12	Air Products Inc	Dibutyl tin dilaurate
	Allentown, PA
PM Acetate	Eastman Chemical	1-methoxy-2-propane acetate
	Kingsport, TN
CAB 551.2	Eastman Chemical	Cellulose acetate butyrate
	Kingsport, TN
Tinuvin 328	Ciba	2-(2-hydroxy-3,5-di-(tert)-amyl phenyl benzotriazole
	Tarrytown, NY
BYK 320	BYK Chemie	Polyether modified methylalklpolysiloxane
	Wallingford, Conn	copolymer
Acrylamac 232-1700	Eastman Chemical	Acrylic polyol
	Kingsport, TN
PolyFox PF6320	Omnova Solutions	Fluorinated polyether
	Akron, OH
Chempol 801-0127	Cook Composite	Coconut oil alkyd polymer
	Polymers
	Kansas City, MO
Duramac 207-2742	Eastman Chemical	Soya oil alkyd polymer
	Kingsport, TN
DINP	CP Hall	Diisonyl phthalate
	Memphis, TN
MAK	Eastman Chemical	Methyl n-amyl ketone
	Kingsport, TN
Desmodur N 3300	Bayer Materials	1,6-hexamethylated diisocyanate based
	Science	polyisocyanate
	Pittsburgh, PA
Bayhydur VP	Bayer Materials	1,6-hexamethylene diisocyanate
LS2336	Science
	Pittsburgh, PA
CE7103	Solutia/UCB	Melamine-formaldehyde resin
	Springfield, MA
PTSA	Cytec Industries, Inc	Cycat 4040 - Paratoluene sulfonic acid solution,
	West Paterson, NJ	40% in isopropanol
Acryflow P120	Lyondell Chemical Co.	Acrylic polyol
	Houston, TX
PolyFox T	Omnova Solutions,	Fluorinated Polyether
	Akron, OH
Paraloid AU608S	Rohm & Haas	Acrylic polyol solution
	Philadelphia, PA
Roskydal 502BA	Bayer Materials	Unsaturated polyester resin in butyl acetate
	Science
	Pittsburgh, PA
Duramac 207-1205	Eastman Chemical	Coconut oil based alkyd
	Kingsport, TN
Slip-AYD SL145E	Elementis Specialties	Paraffin wax emulsion
	Hightstown, NJ
EB49	Specialty Polymers	Acrylic styrene Polymer
	Woodburn, Oregon
SF-69	General Electric	Polydimethylsiloxane
	Waterford, NY
Xylene	Exxon Mobil	Aromatic hydrocarbon
	Houston, TX
Mineral Spirits	Chemcentral	Petroleum hydrocarbon solvent
	Jamestown, NC
Mineral Spirits	Chemcentral	Petroleum hydrocarbon solvent
66/3	Jamestown, NC
DC200	Dow Corning	Polydimethylsiloxane 1000 CST
	Midland, MI
FC129	3M	Potassium fluoroalkyl carboxylate mixture
	St Paul, MN
CP 343-4	Eastman Chemical	25% solution of chlorinated polyolefin in xylene
	Kingsport, TN
NAPA acrylic	Napa auto parts store	Commercial 2K automotive acrylic polyurethane
urethane
MSU 475 Hardner	Napa auto parts store	Commercial 2K automotive polyurethane crosslinker
MPK	Eastman Chemical	Methyl propyl ketone
	Kingsport, TN
SAA	Lyondell Chemical Co	Styrene allyl alcohol
	Houston, TX
Propylene Glycol	Lyondell Chemical Co	1,2-propanediol
	Houston, TX
Natrosol 250	Aqualon/Hercules	Modified hydroxyl ethylcellulose
HHBR PA	Wilmington, DE
Ammonia	Sigma-Aldrich	Ammonium hydroxide
	ST Louis, MO
Chempol 821-3660	Cook Composite	Acrylic modified alkyd dispersion
	Polymers
	Kansas City, MO
Surfynol 104 DPM	Air Products Inc	Acetylenic diol in dipropylene glycol monomethyl
	Allentown, PA	ether
Laponite RDS	Southern Clay	Hydrous sodium lithium magnesium silicate
	Products	modified with tetra sodium pyrophosphate
	Gonzales, TX
CMCAB 641.2	Eastman Chemical	Carboxymethyl cellulose acetate butyrate
	Kingsport, TN
AMP-95	Angus/Dow	2-amino-2-methyl-1-propanol
	Houston, TX
SCT275 Thickener	Rohm & Haas	Polyurethane resin thickening agent solution
	Philadelphia, PA
Tergitol XD	Dow/Union Carbide	Polyalkylene glycol ether
	Houston, TX
Flexipel s-22 WS	Innovative Chemical	Perfluorinated polymer in mineral spirits
	Technologies
	Cartersville, GA
BYK333	BYK Chemie	Polyether modified dimethylpolysiloxane
	Wallingford, Conn
Tint AYD AL505	Elementis Specialties	Burnt Sienna Pigment dispersion in alkyd resin
	Hightstown, NJ
2,2,4-Trimethyl-	Eastman Chemical	Plasticizer/solvent
1,3-pentanediol	Kingsport, TN	(Eastman TXIB)
diisobutyrate
Aromatic 150	Exxon Mobil	Aromatic containing petroleum hydrocarbon
(Same as Solvent	Houston TX
150)
Oxsol 100	Occidental Chemical	Parachlorobenzotrifluoride
	Corp
	Dallas, TX
Astrocure 78	Zircon Corporation	Polyester oligomer
	Collierville, TN
DPGDA	BASF	Dipropylene glycol diacrylate
	Charlotte, NC
Laromer 8967	BASF	Amine modified polyether acrylate
	Charlotte, NC
Laromer PE55F	BASF	Polyester acrylate
	Charlotte, NC
Photomer 6210	Cognis Corp	Aliphatic urethane acrylate
	Ambler, PA
Ebecryl 264	UCB RadCure	Aliphatic urethane triacrylate
	Smyrna, GA
Ebecryl 3212	UCB RadCure	Epoxy acrylate
	Smyrna, GA
Sartomer CN972	Sartomer	Aromatic urethane
	Exton, PA
Actilane 505	Akzo Nobel Resins	Polyester acrylate
	Louisville, KY
Roskydal UA VP	Bayer Materials	Aliphatic urethane acrylate
LS2258	Science
	Pittsburgh, PA
DC 840 resin	Dow Corning	Silicone polymer
	Midland, MI
NuoCure CK	Degussa	Cobalt dryer complex
	Somerset, NJ
Santolink XI100	Solutia	Polyallyl glycidyl ether oligomer
	Springfield, MA
Roskydal 502BA	Bayer Materials	Polyester resin
	Science
	Pittsburgh, PA
Resimene 2040	Solutia/UCB	Styrene allyl alcohol modified methylated melamine
	Springfield, MA	solution
B11P485 Cocoa	Proprietary	Proprietary UV cure stain
UV Stain
Store bought H2O2		Aqueous hydrogen peroxide
Lubrizol	Lubrizol Corp	low molecular weight amine coupled PBU
OS#47550AF	Wickliffe, OH	[Polyisobutylene] succan derivative and is oil free
1X.5LT
Soy salad oil	Alnor oil co	Refined soybean oil
	Valley Stream, NY
Aerosil R972	Degussa	Silane, dichloromethyl rxn products with silica
	Parsippany, NJ
Cycat 296-9	Cytec Industries	Phosphate ester catalyst
	West Paterson, NJ
Nytal 300	R T Vandebilt	Industrial talc
	Norwalk, CT
Eagle Series 2000	Eagle Sales	Burnt Umber tint paste
WB1711 Burnt	ST Louis, MO
Umber
Joncryl 95	S C Johnson Co	Acrylic polymer emulsion
	Sturtevant, WI
Ethylene glycol	Eastman Chemical	Solvent
dibutyl ether	Kingsport, TN
Foamaster S	Cognis	Mineral oil defoamer
	Ambler, PA
Proxel GXL	Avecia	20% solution of 1,2-benzisothiazolin-3-one
	Charlotte, NC
Toluene	Vopak USA	Toluene
	Martinsville, VA
Isobutyl alcohol	Eastman Chemical	2-methyl-1 propanol
	Kingsport, TN
Isopropyl alcohol	Vopak USA	2-propanol
	Martinsville, VA
VM&P Naptha	Vopak USA	Petroleum hydrocarbon distillate
	Martinsville, VA
½ sec NC	Aqualon/Hercules	Cellulose nitrate wet with 2-propanol
	Wilmington, DE
¼ sec NC	Aqualon/Hercules	Cellulose nitrate wet with 2-propanol
	Wilmington, DE
Butyl acetate	Eastman Chemical	Butyl acetate
	Kingsport, TN
GE SF69	General Electric	Polydimethylsiloxane
	Waterford, NY
Paraloid B66	Rohm & Haas	Acrylic polymer
	Philadelphia, PA
N-butyl acetate	Eastman Chemical	Butyl acetate
(same as butyl	Kingsport, TN
acetate)
Ethyl alcohol	Chemcentral	Denatured alcohol - Duplicating fluid 5/95
	Jamestown, NC
n-butyl alcohol	Eastman Chemical	1-butanol
	Kingsport, TN
MEK	Vopak USA	2-butanone
	Martinsville, VA
Santicizer 160	Ferro	Butyl benzyl phthalate
	Walton Hills, OH
TMPTA	BASF	Trimethylol propane triacrylate
	Charlotte, NC
Irgacure 184	Ciba	Hydroxyl cyclohexyl phenyl ketone
	Tarrytown, NY
Solvesso 100 and 150	Exxon Mobil	Aromatic containing petroleum hydrocarbons
	Houston, TX

It will be apparent to those skilled in the relevant art that the disclosed invention may be modified in numerous ways and may assume embodiments other than the preferred form specifically set out and described above. Accordingly, it is intended by the appended claims to cover all modifications of the invention which fall within the true spirit and scope of the invention.